Large‐Scale Conductive Yarns Based on Twistable Korean Traditional Paper (Hanji) for Supercapacitor Applications: Toward High‐Performance Paper Supercapacitors

A simple and scalable method to fabricate a yarn‐type supercapacitor with a large specific capacitance without the aid of traditional pseudocapacitive electrode materials such as conducting polymers and metal oxides is reported. The yarn‐type supercapacitors are made from twisting reduced graphene oxide (rGO) or/and single‐walled carbon nanotubes (SWNTs)‐coated Korean traditional paper (KTP). The yarn‐type paper supercapacitor displays surprisingly enhanced electrochemical capacitance values, showing synergistic effect between rGO and SWNTs (500 times larger than performance of yarn‐type rGO‐coated paper supercapacitors). Coating rGO or/and SWNTs on KTP gives good morphology to the composite film, in which porosity increases and mean pore diameter decreases. The yarn‐type rGO/SWNT paper supercapacitor shows good mechanical strength, high flexibility, excellent electrochemical performance, and long‐life operation. The yarn‐type supercapacitor has an excellent electrochemical performance with a specific capacitance of 366 F g^?1 at scan rate of 25 mV s^?1 and high stability without any degradation in electrical performance up to 10 000 charge–discharge cycles. The average capacitance of rGO/SWNT@KTP yarn‐type supercapacitors is seven times higher than that of sheet‐type supercapacitors at scan rate of 500 mV s^?1. The lighting of a red light‐emitting diode (LED) is demonstrated by the yarn‐type paper supercapacitor without connecting supercapacitors in series.     

Heteroatom‐Doped and Oxygen‐Functionalized Nanocarbons for High‐Performance Supercapacitors

Electrochemical capacitors (best known as supercapacitors) are high‐performance energy storage devices featuring higher capacity than conventional capacitors and higher power densities than batteries, and are among the key enabling technologies of the clean energy future. This review focuses on performance enhancement of carbon‐based supercapacitors by doping other elements (heteroatoms) into the nanostructured carbon electrodes. The nanocarbon materials currently exist in all dimensionalities (from 0D quantum dots to 3D bulk materials) and show good stability and other properties in diverse electrode architectures. However, relatively low energy density and high manufacturing cost impede widespread commercial applications of nanocarbon‐based supercapacitors. Heteroatom doping into the carbon matrix is one of the most promising and versatile ways to enhance the device performance, yet the mechanisms of the doping effects still remain poorly understood. Here the effects of heteroatom doping by boron, nitrogen, sulfur, phosphorus, fluorine, chlorine, silicon, and functionalizing with oxygen on the elemental composition, structure, property, and performance relationships of nanocarbon electrodes are critically examined. The limitations of doping approaches are further discussed and guidelines for reporting the performance of heteroatom doped nanocarbon electrode‐based electrochemical capacitors are proposed. The current challenges and promising future directions for clean energy applications are discussed as well.     

A Layered‐Nanospace‐Confinement Strategy for the Synthesis of Two‐Dimensional Porous Carbon Nanosheets for High‐Rate Performance Supercapacitors

A general approach is developed for the synthesis of 2D porous carbon nanosheets (PCNS) from bio‐sources derived carbon precursors (gelatin) by an integrated procedure of intercalation, pyrolysis, and activation. Montmorillonite with layered nanospace is used as a nanotemplate or nanoreactor to confine and modulate the transformation of gelatin, further leading to the formation of 2D nanosheet‐shaped carbon materials. The as‐made 2D PCNS exhibits a significantly improved rate performance, with a high specific capacitance of 246 F g^?1 and capacitance retention of 82% at 100 A g^?1, being nearly twice that of microsized activated carbon particulates directly from gelatin (131 F g^?1, 44%). The shortened ion transport distance in the nanoscaled dimension and modulated porous structure is responsible for such an enhanced superior rate capability. More importantly, the present strategy can be extended to other bio‐sources to create 2D PCNS as electrode materials with high‐rate performance. This will also provide a potential strategy for configuring 2D nanostructured carbon electrode materials with a short ion transport distance for supercapacitors and other carbon‐related energy storage and conversion devices.     

An Ultrafast Rechargeable Hybrid Sodium‐Based Dual‐Ion Capacitor Based on Hard Carbon Cathodes

Hybrid sodium‐based dual‐ion capacitors (NDICs), which integrate the advantages of supercapacitors and sodium‐ion batteries, have attracted tremendous attention recently. In this work, hybrid sodium‐based dual‐ion capacitors are successfully developed with nitrogen‐doped microporous hard carbon as the cathode and soft carbon as the anode. N‐doping is beneficial to the functional groups, porous structure, and electric conductivity of hard carbon. Hybrid NDICs possess a wide voltage range (0.01–4.7 V), high‐energy density of 245.7 W h kg^?1 at a power density of 1626 W kg^?1, long cycle life (1000 cycles), and outstanding rate performance.     

Fullerene‐Based In Situ Doping of N and Fe into a 3D Cross‐Like Hierarchical Carbon Composite for High‐Performance Supercapacitors

Fullerene‐based carbons are promising electrode materials for supercapacitors due to their unique carbon structures and tunable architectures at the molecular level. By introducing various functional groups with many elements on the fullerene cages, diverse in situ metal/nonmetal‐doped carbon materials with enhanced pseudocapacitances and/or double layer capacitances can be prepared. In the present work, a fullerene derivative, ferrocenylpyrrolidine C₆₀, containing nitrogen and iron, is chosen as the only precursor. A unique microstructure is fabricated by a liquid–liquid interfacial precipitation process. Subsequently, a facile, one‐step annealing of the microstructure at different temperatures is performed. A series of in situ N and Fe‐codoped laminated 3D hierarchical carbon composites in the shape of a cross are successfully synthesized. The as‐prepared N and Fe‐codoped carbon material treated at 700 °C exhibits a high specific capacitance of 505.4 F g^?1 at 0.1 A g^?1. To the best knowledge, this is the highest supercapacitor capacitance based on fullerene electrode materials. The use of a fullerene derivative as an in‐situ doped carbon for applications in energy storage opens a new avenue for developing future synthetic strategies to extend the repertoire of electrode materials with high performance.     

Structure‐Controlled,Vertical Graphene‐Based,Binder‐Free Electrodes from Plasma‐Reformed Butter Enhance Supercapacitor Performance

Vertical graphene nanosheets (VGNS) hold great promise for high‐performance supercapacitors owing to their excellent electrical transport property, large surface area and in particular, an inherent three‐dimensional, open network structure. However, it remains challenging to materialise the VGNS‐based supercapacitors due to their poor specific capacitance, high temperature processing, poor binding to electrode support materials, uncontrollable microstructure, and non‐cost effective way of fabrication. Here we use a single‐step, fast, scalable, and environmentally‐benign plasma‐enabled method to fabricate VGNS using cheap and spreadable natural fatty precursor butter, and demonstrate the controllability over the degree of graphitization and the density of VGNS edge planes. Our VGNS employed as binder‐free supercapacitor electrodes exhibit high specific capacitance up to 230 F g^?1 at a scan rate of 10 mV s^?1 and >99% capacitance retention after 1,500 charge‐discharge cycles at a high current density, when the optimum combination of graphitic structure and edge plane effects is utilised. The energy storage performance can be further enhanced by forming stable hybrid MnO₂/VGNS nano‐architectures which synergistically combine the advantages from both VGNS and MnO₂. This deterministic and plasma‐unique way of fabricating VGNS may open a new avenue for producing functional nanomaterials for advanced energy storage devices.     

Nitrogen‐Doped Wrinkled Carbon Foils Derived from MOF Nanosheets for Superior Sodium Storage

Preparation of hierarchical carbon nanomaterials from metal?organicframeworks (MOFs) offers immense potential in the improvement of energy density, tunability, and stability of functional materials for energy storage and conversion. How interconnected nitrogen (N)‐doped wrinkled carbon foils derived from MOF nanosheets can serve as high‐performance sodium storage materials due to their multiscale porous structure is shown here. The novel N‐doped carbon nanomaterials are synthesized through the pyrolysis of 2D Mn‐based MOFs, which are produced through the assistance of monodentate ligands to enable the planar growth of MOFs. Subsequent acid etching creates hierarchical pores and channels to allow rapid ion transport. The resulting materials achieve high‐rate capability (165 and 150 mA h g^?1 at current densities of 8 and 10 A g^?1, respectively) and high stability (capacity retention 72.8% after 1000 cycling at 1.0 A g^?1), when they are used as anode in sodium‐ion capacitors.     

Flexible and Wearable All‐Solid‐State Supercapacitors with Ultrahigh Energy Density Based on a Carbon Fiber Fabric Electrode

Wearable textile energy storage systems are rapidly growing, but obtaining carbon fiber fabric electrodes with both high capacitances to provide a high energy density and mechanical strength to allow the material to be weaved or knitted into desired devices remains challenging. In this work, N/O‐enriched carbon cloth with a large surface area and the desired pore volume is fabricated. An electrochemical oxidation method is used to modify the surface chemistry through incorporation of electrochemical active functional groups to the carbon surface and to further increase the specific surface area and the pore volume of the carbon cloth. The resulting carbon cloth electrode presents excellent electrochemical properties, including ultrahigh areal capacitance with good rate ability and cycling stability. Furthermore, the fabricated symmetric supercapacitors with a 2 V stable voltage window deliver ultrahigh energy densities (6.8 mW h cm^?3 for fiber‐shaped samples and 9.4 mW h cm^?3 for fabric samples) and exhibit excellent flexibility. The fabric supercapacitors are further tested in a belt‐shaped device as a watchband to power an electronic watch for ≈9 h, in a heart‐shaped logo to supply power for ≈1 h and in a safety light that functions for ≈1 h, indicating various promising applications of these supercapacitors.     

Anatase TiO2 Confined in Carbon Nanopores for High‐Energy Li‐Ion Hybrid Supercapacitors Operating at High Rates and Subzero Temperatures

Li‐ion hybrid supercapacitors (Li‐HSCs) hold great promise in future electrical energy storage due to their relatively high power and energy density. However, a major challenge lies in the slow kinetics of Li‐ion intercalation/extraction within metal‐oxide electrodes. Here, it is shown that ultrafast charge storage is realized by confining anatase TiO₂ nanoparticles in carbon nanopores to enable a high‐rate anode for Li‐HSCs. The porous carbon with interconnected pore walls and open channels not only works as a conductive host to protect TiO₂ from structural degradation but also provides fast pathways for ion/electron transport. As a result, the assembled cells exhibit remarkable rate capabilities with a specific capacity of ≈140 mAh g^?1 at a slow charge and ≈60 mAh g^?1 at a 3.5 s fast charge. While the charge/discharge process can be completed as fast as that of state‐of‐the‐art electrical double‐layer capacitors (EDLCs), the produced nanocomposites show three to seven times higher volumetric capacitance than activated carbons used in commercial EDLCs with acetonitrile‐based electrolytes. Equally important for some applications in cold climates or the space, the Li‐HSCs can operate at subzero temperatures as low as ?40 °C, which is likely only limited by thermal properties of the acetonitrile (melting point of ?45 °C).     

High Volumetric Capacitance,Ultralong Life Supercapacitors Enabled by Waxberry‐Derived Hierarchical Porous Carbon Materials

Supercapacitors with fast charge/discharge rate and long cycling stability (>50 000 cycles) are attractive for energy storage and mobile power supply. In this paper, a facile strategy is developed to fabricate an Fe₂O₃/FeS‐decorated N, S‐codoped hierarchical porous carbon hybrid. Its microstructure and compositions can be readily controlled through adjusting the hydrothermal reaction between waxberry and iron sulfate. The constructed supercapacitors with the as‐prepared carbon materials from this reaction are able to exhibit outstanding capacitive performance with a superfast charge/discharge rate (<1 s), ultralong cycle life (>50 000 cycles, 80 A g⁻¹), ultrahigh volumetric capacitance (1320.4 F cm⁻³, 0.1 A g⁻¹), and high energy density (100.9 W h kg⁻¹, 221.9 W h L⁻¹). The outstanding performance makes it one of the best biomass‐derived supercapacitors. The superior capacitive behavior is likely to arise from the N and S codoping on the surface/edge/skeleton of the carbon microspheres and nanosheet composites coupled with the fast redox reaction of Fe₂O₃/FeS. Overall, this research presents a new avenue for developing the next generation of sustainable high‐performance energy storage device.     

Recent Progress in Biomass‐Derived Electrode Materials for High Volumetric Performance Supercapacitors

Tremendous efforts have been spent on the development of electrical energy storage (EES) systems with high volumetric performance in the past few years due to the evergrowing demand of miniaturized, portable electronic devices, and electric vehicles. Among all the EES devices, supercapacitors with electrode materials derived from biosources have attracted special attention due to their eco‐friendliness, natural abundance, their intrinsic porous structures as well as their renewable and sustainable features. However, the relatively low packing densities make their specific volumetric capacitance intrinsically low, which has largely limited their further application in the supercapacitors. To address these issues, various promising approaches ranging from structural manufacture to compositional design are applied and significant breakthroughs are witnessed in recent years. In this progress report, key factors influencing the volumetric performance of biomass‐derived electrode materials are systematically discussed with a particular focus spanning from fundamental to operational aspects. This work provides insights into the development of high‐volumetric‐performance biomass‐derived supercapacitors by comprehensively summarizing recent advances in the rational structural design and fabrication. Perspectives regarding the future challenges and promising research directions on the design of next‐generation EES devices are also provided.     

Flexible Nano‐felts of Carbide‐Derived Carbon with Ultra‐high Power Handling Capability

Nano‐fibrous felts (nano‐felts) of carbide‐derived carbon (CDC) have been developed from the precursor of electrospun titanium carbide (TiC) nano‐felts. Conformal transformation of TiC into CDC conserves main features of the precursor including the high interconnectivity and structural integrity; the developed TiC‐CDC nano‐felts are mechanically flexible/resilient, and can be used as electrode material for supercapacitor application without the addition of any binder. After synthesis through chlorination of the precursor at 600 °C, the TiC‐CDC nano‐fibers show an average pore size of ～1nm, a high specific surface area of 1390 m²/g; and the nano‐fibers have graphitic carbon ribbons embedded in a highly disordered carbon matrix. Graphitic carbon is preserved from the precursor nano‐fibers where a few graphene layers surround TiC nanocrystallites. Electrochemical measurements show a high gravimetric capacitance of 110 F/g in aqueous electrolyte (1 M H₂SO₄) and 65 F/g in organic electrolyte (1.5 M TEA‐BF₄ in acetonitrile). Because of the unique microstructure of TiC‐CDC nano‐felts, a fade of the capacitance of merely 50% at a high scan rate of 5 V/s is observed. A fade of just 15% is observed for nano‐felt film electrodes tested in 1 M H₂ SO₄ at 1 V/s, resulting in a high gravimetric capacitance of 94 F/g. Such a high rate performance is only known for graphene or carbon‐onion based supercapacitors, whereas binders have to be used for the fabrication of those supercapacitors.     

Battery‐like Supercapacitors from Vertically Aligned Carbon Nanofiber Coated Diamond: Design and Demonstrator

To fabricate battery‐like supercapacitors with high power and energy densities, big capacitances, as well as long‐term capacitance retention, vertically aligned carbon nanofibers (CNFs) grown on boron doped diamond (BDD) films are employed as the capacitor electrodes. They possess large surface areas, high conductivity, high stability, and importantly are free of binder. The large surface areas result from their porous structures. The containment of graphene layers and copper metal catalysts inside CNFs leads to their high conductivity. Both electrical double layer capacitors (EDLCs) in inert solutions and pseudocapacitors (PCs) using Fe(CN)₆^3?/4? redox‐active electrolytes are constructed with three‐ and two‐electrode systems. The assembled two‐electrode symmetrical supercapacitor devices exhibit capacitances of 30 and 48 mF cm^?2 at 10 mV s^?1 for EDLC and PC devices, respectively. They remain constant even after 10 000 charging/discharging cycles. The power densities are 27.3 and 25.3 kW kg^?1 for EDLC and PC devices, together with their energy densities of 22.9 and 44.1 W h kg^?1, respectively. The performance of these devices is superior to most of the reported supercapacitors and batteries. Vertically aligned CNF/BDD hybrid films are thus useful to construct high‐performance battery‐like and industry‐orientated supercapacitors for future power devices.     

Large‐Area,Ultrathin Inorganic Network Coverages–Graphene Hierarchical Electrodes for Flexible,Heat‐Resistant Energy Storage Application

Graphene and quasi‐2D graphene‐like materials with an ultrathin thickness have been investigated as a new class of nanoscale materials due to their distinctive properties. A novel “molecular tools‐assistances” strategy is developed to fabricate two kinds of graphene‐based electrodes, ultrathin Fe‐doped MnO₂ network coverage–graphene composites (G‐MFO) and ultrathin MoS₂ network coverage–graphene composites (G‐MoS₂) with special hierarchical structures. Such structures enable a large contact interface between the active materials and graphene and thus fully exploit the synergistic effect from both the high specific capacitance of MFO or MoS₂ and the superb conductivity of graphene. Benefiting from their unique structural features, G‐MFO and G‐MoS₂ films directly use as free‐standing electrodes for flexible asymmetric supercapacitors with a nonaqueous gel electrolyte. The device achieves a high energy/power density, superior flexibility, good rate capability as well as outstanding performance stability even at a high temperature. This work represents a promising prototype to design new generation of hybrid supercapacitors for future energy storage devices.     

Sandwich‐Type Microporous Carbon Nanosheets for Enhanced Supercapacitor Performance

Sandwich‐type microporous hybrid carbon nanosheets (MHCN) consisting of graphene and microporous carbon layers are fabricated using graphene oxides as shape‐directing agent and the in‐situ formed poly(benzoxazine‐co‐resol) as carbon precursor. The reaction and condensation can be readily completed within 45 min. The obtained MHCN has a high density of accessible micropores that reside in the porous carbon with controlled thickness (e.g., 17 nm), a high surface area of 1293 m² g^?1 and a narrow pore size distribution of ca. 0.8 nm. These features allow an easy access, a rapid diffusion and a high loading of charged ions, which outperform the diffusion rate in bulk carbon and are highly efficient for an increased double‐layer capacitance. Meanwhile, the uniform graphene percolating in the interconnected MHCN forms the bulk conductive networks and their electrical conductivity can be up to 120 S m^?1 at the graphene percolation threshold of 2.0 wt.%. The best‐practice two‐electrode test demonstrates that the MHCN show a gravimetric capacitance of high up to 103 F g^?1 and a good energy density of ca. 22.4 Wh kg^?1 at a high current density of 5 A g^?1. These advanced properties ensure the MHCN a great promise as an electrode material for supercapacitors.     

Ultrafine Metal Nanoparticles/N‐Doped Porous Carbon Hybrids Coated on Carbon Fibers as Flexible and Binder‐Free Water Splitting Catalysts

By employing in situ reduction of metal precursor and metal‐assisted carbon etching process, this study achieves a series of ultrafine transition metal‐based nanoparticles (Ni–Fe, Ni–Mo) embedded in N‐doped carbon, which are found efficient catalysts for electrolytic water splitting. The as‐prepared hybrid materials demonstrate outstanding catalytic activities as non‐noble metal electrodes rendered by the synergistic effect of bimetal elements and N‐dopants, the improved electrical conductivity, and hydrophilism. Ni/Mo₂C@N‐doped porous carbon (NiMo‐polyvinylpyrrolidone (PVP)) and NiFe@N‐doped carbon (NiFe‐PVP) produce low overpotentials of 130 and 297 mV at a current density of 10 mA cm^?2 as catalysts for hydrogen evolution reaction and oxygen evolution reaction, respectively. In addition, these binder‐free electrodes show long‐term stability. Overall water splitting is also demonstrated based on the couple of NiMo‐PVP||NiFe‐PVP catalyzer. This represents a simple and effective synthesis method toward a new type of nanometal–carbon hybrid electrodes.     

A Three‐Dimensionally Interconnected Carbon Nanotube–Conducting Polymer Hydrogel Network for High‐Performance Flexible Battery Electrodes

High‐performance flexible energy‐storage devices have great potential as power sources for wearable electronics. One major limitation to the realization of these applications is the lack of flexible electrodes with excellent mechanical and electrochemical properties. Currently employed batteries and supercapacitors are mainly based on electrodes that are not flexible enough for these purposes. Here, a three‐dimensionally interconnected hybrid hydrogel system based on carbon nanotube (CNT)‐conductive polymer network architecture is reported for high‐performance flexible lithium ion battery electrodes. Unlike previously reported conducting polymers (e.g., polyaniline, polypyrrole, polythiophene), which are mechanically fragile and incompatible with aqueous solution processing, this interpenetrating network of the CNT‐conducting polymer hydrogel exibits good mechanical properties, high conductivity, and facile ion transport, leading to facile electrode kinetics and high strain tolerance during electrode volume change. A high‐rate capability for TiO₂ and high cycling stability for SiNP electrodes are reported. Typically, the flexible TiO₂ electrodes achieved a capacity of 76 mAh g^–1 in 40 s of charge/discharge and a high areal capacity of 2.2 mAh cm^–2 can be obtained for flexible SiNP‐based electrodes at 0.1C rate. This simple yet efficient solution process is promising for the fabrication of a variety of high performance flexible electrodes.     

Stable Nano‐Encapsulation of Lithium Through Seed‐Free Selective Deposition for High‐Performance Li Battery Anodes

Metallic lithium has long been deemed as the ultimate anode material for future high‐energy‐density Li batteries. However, the commercialization of Li metal anodes remains hindered by some major hurdles including their huge volume fluctuation during cycling, unstable solid electrolyte interface (SEI), and dendritic deposition. Herein, the concept of nano‐encapsulating electrode materials is attempted to tackle these problems. Nitrogen‐doped hollow porous carbon spheres (N‐HPCSs), prepared via a facile and low‐cost method, serve as the nanocapsules. Each N‐HPCS has a lithophilic carbon shell with a thin N‐rich denser layer on its inner surface, which enables preferential nucleation of Li inside the hollow sphere. It is demonstrated by in situ electron microscopy that these N‐HPCS hosts allow Li to be encapsulated in a highly reversible and repeatable manner. Ultralong Li filling/stripping cycling inside single N‐HPCSs is achieved, up to 50 cycles for the first time. Li ion transport across multiple connected N‐HPCSs, leading to long‐range Li deposition inside their cavities, is visualized. In comparison, other types of carbon spheres with modified shell structures fail in encapsulating Li and dendrite suppression. The necessity of the specific shell design is therefore confirmed for stable Li encapsulation, which is essential for the N‐HPCS‐based anodes to achieve superior cycling performance.     

Freestanding and Sandwich‐Structured Electrode Material with High Areal Mass Loading for Long‐Life Lithium–Sulfur Batteries

Freestanding cathode materials with sandwich‐structured characteristic are synthesized for high‐performance lithium–sulfur battery. Sulfur is impregnated in nitrogen‐doped graphene and constructed as primary active material, which is further welded in the carbon nanotube/nanofibrillated cellulose (CNT/NFC) framework. Interconnected CNT/NFC layers on both sides of active layer are uniquely synthesized to entrap polysulfide species and supply efficient electron transport. The 3D composite network creates a hierarchical architecture with outstanding electrical and mechanical properties. Synergistic effects generated from physical and chemical interaction could effectively alleviate the dissolution and shuttling of the polysulfide ions. Theoretical calculations reveal the hydroxyl functionization exhibits a strong chemical binding with the discharge product (i.e., Li₂S). Electrochemical measurements suggest that the rationally designed structure endows the electrode with high specific capacity and excellent rate performance. Specifically, the electrode with high areal sulfur loading of 8.1 mg cm^?2 exhibits an areal capacity of ≈8 mA h cm^?2 and an ultralow capacity fading of 0.067% per cycle over 1000 discharge/charge cycles at C/2 rate, while the average coulombic efficiency is around 97.3%, indicating good electrochemical reversibility. This novel and low‐cost fabrication procedure is readily scalable and provides a promising avenue for potential industrial applications.     

Free‐Standing 3D Nanoporous Duct‐Like and Hierarchical Nanoporous Graphene Films for Micron‐Level Flexible Solid‐State Asymmetric Supercapacitors

High energy density and power density within a limited volume of flexible solid‐state supercapacitors are highly desirable for practical applications. Here, free‐standing high‐quality 3D nanoporous duct‐like graphene (3D‐DG) films are fabricated with high flexibility and robustness as the backbones to deposit flower‐like MnO₂ nanosheets (3D‐DG@MnO₂). The 3D‐DG is the ideal support for the deposition of large amount of active materials because of its large surface area, appropriate pore structure, and negligible volume compared with other kinds of carbon backbones. Moreover, the 3D‐DG preserve the distinctive 2D coherent electronic properties of graphene, in which charge carriers move rapidly with a small resistance through the high‐quality and continuous chemical vapor deposition‐grown graphene building blocks, which results in a high rate performance. Marvelously, ultrathin (≈50 μm) flexible solid‐state asymmetric supercapacitors (ASCs) using 3D‐DG@MnO₂ as the positive electrode and 3D hierarchical nanoporous graphene films as the negative electrode display ultrahigh volumetric energy density (28.2 mW h cm^?3) and power density (55.7 W cm^?3) at 2.0 V. Furthermore, as‐prepared ASCs show high cycle stability clearly demonstrating their broad applications as power supplies in wearable electronic devices.